Novel stable ytterbium acetylacetonate-quinaldinate complexes as single-molecule magnets and surprisingly efficient luminophores

Dalton Transactions. 2023. Vol. 52. No. 47. P. 17911–17927.

Taydakov I., Gavrikov A., Metlin M., Buzoverov M., Efimov N.

The first Yb complexes comprising a quinoline-2-carboxylate (quinaldinate, Q−) ligand, namely 1D-polymeric [Yb(acac)2(Q)]n (1, acac− is the acetylacetonate (pentane-2,4-dionate) anion) and mononuclear [Yb(acac)2(Q)(Phen)] (2, Phen is 1,10-phenanthroline), are reported. The bifunctionality of both complexes as field-induced single-molecule magnets (SMMs) and near IR luminophores has been revealed. The SMM properties of 1 and 2 have been discussed in terms of the geometry and composition of the coordination environment. Also, 1 is the first example of 1D-polymeric SMMs with the capped octahedral surrounding of Yb3+. The photoluminescence quantum yields (PLQYs) of 1 and 2 are 2 and 4%, respectively. The origins of this difference are discussed. Surprisingly, the PLQY value of 2 is high for compounds comprising a lot of C-H vibrational quenchers, being the highest one for reliably characterized Yb β-diketonate complexes, and surpassing those for complexes with a broad range of anionic ligands. In this respect, the role of the Phen ligand is to tune the coordination mode of Q− thereby decreasing the energy of coordinating C-O oscillators rather than to act as a typical antenna ligand. These results can give rise to an alternative route to elaborate efficient Yb-based luminophores via the substitution of the β-diketonate ligands controlled by the introduction of appropriate neutral ligands.

Keywords: coordination compounds, luminescence, 1,3-diketones